Monolayers of organic compounds on metal oxide surfaces or metal surfaces containing oxide and component produced therewith based on organic electronics

ABSTRACT

Monolayers of organic compounds are formed on transparent conductive metal oxide surfaces these are used for example in producing organically based electronic components. By selecting the monolayer, the service life of the devices produced therewith may be improved by orders of magnitude.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on and hereby claims priority to InternationalApplication No. PCT/EP2010/052700 filed on Mar. 3, 2010 and GermanApplication No. 10 2009 012 163.3 filed on Mar. 6, 2009, the contents ofwhich are hereby incorporated by reference.

BACKGROUND

The invention relates to a novel selection for monolayers of organicdielectric compounds particularly on transparent conductive metal oxidesurfaces or oxide-containing metal surfaces, as used, for example, inthe production of organic-based electronic components.

For the purposes of market introduction of OLEDs (organic light-emittingdiodes) and/or OLEECs (organic light-emitting electrochemical cells), itis particularly advantageous to use monolayers with precisely adjustedfunctionality in electronic components to increase the lifetime,especially also in organic electronic components. In order thatmolecules in monolayers self-assemble and thus exhibit very highfunctionality and functional density, it is advisable to fix them to theparticular electrodes by head or anchor groups, which results inautomatic alignment of the linker groups, i.e. of the groups connectingthe two ends. The attachment to the substrate takes place spontaneouslyprovided that the substrate has been prepared appropriately.

The specific functionality is determined by the linkers and head groups.The anchor determines the self-assembly.

For this purpose, a known example from DE 10 2004 005 082 is an aromatichead group with π-π interaction, the introduction of which is chemicallycomplex, and which binds a self-assembly dielectric layer to anelectrode. The binding to the counterelectrode, the so-called anchorgroup of the organic dielectric compound which is usable as a monolayerin a capacitor, according to DE 10 2004 005 082 is a silane compoundwhich can be bound to the electrode via an oxide layer formed from anon-copper oxide.

Asha Sharma, Bernard Kippelen, Peter J. Hotchkiss, and Seth R. Marder,“Stabilization of the work function of indium tin oxide using organicsurface modifiers in organic light-emitting diodes”, Applied PhysicsLetters 93 (2008) 163308, discloses that it is possible using phosphonicacids to produce highly fluorinated SAM monolayers from the liquidphase.

It is demonstrated therein that at least partly fluorinated compoundsexert a stabilizing effect on the ITO interface. For example, thestabilizing effect of specific SAM molecules for the increase inlifetime in efficient organic light-emitting diodes is also demonstratedgraphically therein.

A disadvantage of the known related art is that the electrode surface,to apply the self-assembly monolayer (SAM), is preferably eitherfunctionalized or at least a considerable material excess from theliquid phase is employed, in order to achieve the desired effectiveness.

SUMMARY

It is therefore one possible object to overcome the disadvantages of therelated art and to provide a layer of SAM molecules which likewiseincreases the lifetime of the organic electronic light-emitting cells,preferably self-emitting components, but which is producible with smallamounts on the electrode.

The inventors propose for the use of fluorinated silanes on transparentconductive metal oxide surfaces or oxide-containing metal surfaces,wherein the binding to the metal oxide surface is via the silane group.The invention also provides a process for producing a monolayer on atransparent conductive metal oxide layer, wherein a fluorinatedstraight-chain silane compound which binds to the metal oxide layer bythe silane end is deposited from the gas phase. Finally, the inventionprovides an SAM layer produced from fluorinated silanes on a transparentconductive metal oxide layer, wherein the silanes are bound to the metaloxide surface from the gas phase.

The general finding of the invention is that not only ITO surfaces butalso quite generally transparent conductive metal oxide (TCO) surfacescan be optimized by fluorinated compounds. An additional finding of theinvention is that silanes can be used to bind these fluorinatedcompounds to the surfaces in an inexpensive manner. In contrast to theknown compounds which anchor via phosphorus, the silanes can also bedeposited without a liquid phase, which is both material-gentle (mostdepositions from liquids are performed by dip coating, by immersing thefinished ITO layer) and material-saving.

The use of fluorinated silanes on dielectric surfaces is already triedand trusted, but it has always been assumed to date that the SAMs havean insulating effect on conductive surfaces and are thereforetroublesome in the component. It has now been found that, surprisingly,the SAMs, which belong to the group of insulators, have goodconductivities for charge carriers, especially for holes. The layerstructure composed of TCO layer, SAM and hole conductor or electroninjection layer, presented here for the first time leads to improvedproperties of the overall component in relation to energy efficiency,stability, etc., as has been shown here.

As shown experimentally, the material class of the fluorinated silaneshas good adhesion to TCOs, especially ITO. These materials arecommercially available and comparatively inexpensive (table 1). Ifrelatively large containers are purchased, the costs can quite possiblybe lowered by a factor of 10.

TABLE 1 Preferred materials for formation of the self-assembly monolayeraccording to the present invention, which simultaneously increases holeinjection and improves the lifetime of the components. TrichlorosilaneAB110562 (3,3,3-Trifluor- 10 g 41.60 ε [592-09-6] C3H4Cl3F3Siopropyl)trichlorosilane; 97% AB182091 Nonafluorohexyltrichloro- 10 g35.10 ε [78560-47-1] C6H4Cl3F9Si silane; 95% AB111444(Tridecafluoro-1,1,2,2- 10 g 36.40 ε [78560-45-9] C8H4Cl3F13Sitetrahydrooctyl)trichlorosilane; 97% AB103609 1H,1H,2H,2H-  5 g 46.20 ε[78560-44-8] C10H4Cl3F17Si Perfluorodecyltrichloro- silane; 97% AB2319511H,1H,2H,2H-  1 g 64.80 ε [102488-50-6] C14H4Cl3F25Si Perfluorotetrade-cyltrichlorosilane; 97% Ethoxysilane AB252596Nonafluorohexyltriethoxysilane 25 g 72.80 ε [102390-98-7] C12H19F9O3SiAB104055 1H,1H,2H,2H-  5 g 45.20 ε [51851-37-7] C14H19F13O3SiPerfluorooctyltriethoxysilane; 97% AB172273 1H,1H,2H,2H-  5 g 46.00 ε[101947-16-4] C16H19F17O3Si Perfluorodecyltriethoxy- silane; 97%Methoxysilane AB111473 (3,3,3-  5 g 24.70 ε [429-60-7] C6H13F3O3SiTrifluoropropyl)trimethoxysilane; 97% AB153265 (Tridecafluoro-1,1,2,2,-10 g 48.10 ε [85857-16-5] C11H13F13O3Sitetrahydrooctyl)trimethoxysilane; 95% packaged over copper powderAB153340 (Heptadecafluoro-  5 g 54.60 ε [83048-65-1] C13H13F17O3Si1,1,2,2- tetrahydrodecyl)trimethoxysilane; 95%

These have the general formula 1:

where R₁ and R₂ are each independently Cl or alkoxy, especially methoxy,ethoxy or OH.

X may be O, S, NH or absent; n is in the range from 0 to 5 and ispreferably 0; m is from 0 to 20, especially from 5 to 10.

Formula 1 can be extended as shown below, such that ether units arebetween the individual constituents of the molecule chain; moreparticularly, h and f would then preferably be 2 or are generallybetween 1 and 4; X₁, X₂ and X₃ may each independently be O, S, NH, ahalogen (F) or even absent; n is in the range from 0 to 2 and ispreferably 0; m is from 0 to 15, especially between 2 and 5. The CF₃group at the end of the molecule chain can also be omitted. In thiscase. X₃═F.

These compounds are preferably processed from the gas phase in amaterial-saving manner, which in the simplest case requires merely atemperature-controlled vacuum chamber. The substrates are preferably notactivated by an RIE treatment with oxygen with sputtering properties,since saturation of the crystal lattice with oxygen should be avoided. Acorresponding gentle treatment is intended to remove only organicimpurities. It is usually sufficient to clean with common solvents(water, alcohols such as ethanol or organic solvents: NMP,dimethylformamide, dimethyl sulfoxide, toluene, chlorinated solventssuch as chloroform, chlorobenzene, dichloromethane, ethers such asdiethyl ether, tetrahydrofuran, dioxane, or esters such as ethylacetate, methoxypropyl acetate, etc.). One option is an argonback-sputtering operation. The TCO—OSi bond is so strong that it evenundermines minor soiling in the sub-monolayer region. This soiling canoptionally be rinsed off with the solvents mentioned after thedeposition. The processing of the SAM without solvating solvents givesvery stable monolayers with good adhesion.

The following processes not specified in a restrictive manner arepossible:

-   -   a. In batch processes which allow high parallelism. Subsequent        handling of the substrates under air does not damage the        coating.    -   b. In production plants there are back-sputtering units which        can be used to apply the silanes from the gas phase after the        cleaning.    -   c. All CVD (Chemical Vapor Deposition) and ALD (Atomic Layer        Deposition) systems.

A preference for deposition from the gas phase does not rule outdeposition from liquid phase. The highly reactive silanes, however, thenhave to be processed preferably from dried aprotic solvents. Since theseare hygroscopic, the solutions do not have prolonged stability underair.

Within the context of the invention are not only transparent conductiveelectrodes based on indium tin oxide, but also other conductiveelectrodes, for example aluminum-doped zinc oxide. In the case ofinverted diodes, the anode may also be formed of nontransparent metalswith a native oxide surface. Examples here would be titanium, aluminum,nickel, etc.

The monolayer according to the invention is followed, in the stackstructure of the organic electronic component, for example of the OLEDor of the OLEEC, by a hole conductor layer.

For the hole conductor layer, the following materials are mentioned byway of example but in a nonrestrictive manner:

-   -   N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-dimethylfluorene    -   N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-diphenylfluorene    -   N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-diphenylfluorene    -   N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-2,2-dimethylbenzidine    -   N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-spirobifluorene    -   2,2′,7,7′-tetrakis(N,N-diphenylamino)-9,9′-spirobifluorene    -   N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine    -   N,N′-bis(naphthalen-2-yl)-N,N′-bis(phenyl)benzidine    -   N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine    -   N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-dimethylfluorene    -   N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-spirobifluorene    -   Di-cyclohexane    -   2,2′,7,7′-tetra(N,N-ditolyl)aminospirobifluorene    -   9,9-bis-9H-fluorene    -   2,2′,7,7′-tetrakis-9,9-spirobifluorene    -   2,7-bis-9,9-spirobifluorene    -   2,2′-bis-9,9-spirobifluorene    -   N,N′-bis(phenanthren-9-yl)-N,N′-bis(phenyl)benzidine    -   N,N,N′,N′-tetranaphthalen-2-ylbenzidine    -   2,2′-bis(N,N-diphenylamino)-9,9-spirobifluorene    -   9,9-bis-9H-fluorene    -   9,9-bis-9H-fluorene    -   Titanium oxide phthalocyanine    -   Copper phthalocyanine    -   2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane    -   4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine    -   4,4′,4″-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine    -   4,4′,4″-tris(N-(1-naphthyl)-N-phenylamino)triphenylamine    -   4,4′,4″-tris(N,N-diphenylamino)triphenylamine    -   Pyrazino phenanthroline-2,3-dicarbonitrile    -   N,N,N′,N′-tetrakis(4-methoxyphenyl)benzidine    -   2,7-bis-9,9-spirobifluorene    -   2,2′-bis-9,9-spirobifluorene    -   N,N′-di(naphthalen-2-yl)-N,N′-diphenylbenzene-1,4-diamine    -   N,N′-diphenyl-N,N′-di-benzidine    -   N,N′-diphenyl-N,N′-di-benzidine    -   Tri(diphenylbenzimidazoyl)iridium(III) DPBIC.

These hole transport layers may be doped or undoped. The dopants usedare strong acceptors, such as copper salts, F4-TCNQs(tetrafluorotetracyanoquinodimethanes) or derivatives thereof. Likewisesuitable are oxides such as molybdenum oxides, tungsten oxides orrhenium oxides.

It has been demonstrated experimentally that the cause of the initialdecline in lifetime in an organic light-emitting diode is thedegradation of the interface between the oxygen-laden indium tin oxideelectrode and the hole transport material. It is exactly here that theimprovement achieved by the present invention intervenes, since thesurprising conductivity of the SAM layer for holes eliminates thisinterface of the TCO with the hole conductor layer without impairing theperformance of the component.

The oxygen loading serves to adjust the work function of the anode.Compared to the related art, the proposed self-assembly monolayers offerthe following advantages:

-   -   high work functions without RIE pretreatment    -   inexpensive materials    -   processing from the gas phase    -   increase in the lifetime of the organic component and complete        avoidance of the initial decline in lifetime in luminance and        voltage rise and power efficiency.

In contrast to the related art, all advantages are fulfilled at the sametime here. As shown in the examples, the selection of possible moleculeclasses is very limited. A variation in the anchor groups was alsostudied. The silane anchor group used here appears to be ideal for theuse of indium tin oxide surfaces.

EXAMPLE 1 Pretreatment of the ITO Anode

The reference used is the standard pretreatment. For this purpose, aglass plate coated with 150 nm of indium tin oxide is exposed to anoxygen plasma for 10 min. The plasma with a 500 W HF output at an oxygenpressure of 0.6 mbar burns directly over the substrate. Thecharacteristics of a diode whose substrate has been treated in such away are shown in red in graphs below. This pretreatment is necessary inorder that the proposed diode and the reference diode have approximatelythe same performance data in order to be able to better compare themwith one another.

EXAMPLE 2

A substrate analogously to example 1 is exposed in a reactor with atwo-chamber system to a gentle cleaning step at 250 W HF power for 10min. The plasma burns in one chamber and the substrate is in the secondchamber not flooded with plasma. The pressure in the substrate chamberis 0.5 mbar. In this way, it is possible to very gently remove organicimpurities. Sputtering effects and incorporation of oxygen into thecrystal lattice do not occur. Normally, such a pretreatment isinsufficient for efficient organic light-emitting diodes. Thereafter, aself-assembly monolayer containing the perfluorodecyltrichlorosilanereagent was deposited.

For this purpose, a commercial system for molecular vapor deposition wasused, which is already used globally in companies and research centers,the MVD100 system from Applied MST (http://www.appliedmst.com/productsmvd100.htm pdf “Overview” and “Features”). This is formed from a vacuumchamber in which the substrates can be positioned, which is connected toa second chamber in which the oxygen plasma is ignited. This means thatthe ions are not accelerated directly onto the substrate. The duration,HF power and gas flow rate can be varied. Three gas feed lines are usedto pass the substances to be deposited and a catalyst, in this casewater vapor, into the main chamber. In three preliminary chambers, thenecessary pressure can be generated and the necessary temperature can beestablished in order to convert the substances to the gas phase. For thedeposition of one layer of perfluoro-, decyl-, trichlorosilane, achamber pressure of 0.6 mbar is established. The reaction time is 900sec. Subsequently, at 8 mbar, water vapor is used to catalyze thebinding and crosslinking. This method of deposition does not require anyfurther aftertreatment; the diode can be applied directly to the SAMsubstrate.

The characteristic for a diode which has been assembled on thissubstrate is shown in black.

EXAMPLE 3

A long-known diode includes NPB hole conductor(N,N′-bis(naphthalen-2-yl)-N,N′-bis(phenyl)benzidine) and the electronconductor Alq (tris(8-hydroxyquinolinolato)aluminum). For this purpose,40 nm of NBP and 40 nm of Alq are deposited from the gas phase. Thecathode is formed by a layer of 0.7 nm of lithium fluoride and 200 nm ofaluminum.

The SAM layer of fluorinated silanes on the conductive metal oxide layerconnects this layer to a hole conduction or electron injection layerwithout formation of a direct interface between these layers. Thisallows all faults which arise from the formation of these interfaces tobe avoided.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other objects and advantages of the present invention willbecome more apparent and more readily appreciated from the followingdescription of the preferred embodiments, taken in conjunction with theaccompanying drawings of which:

FIG. 1 shows the luminance (right-hand axis) and the currentcharacteristic (left-hand axis) of two identically produced NPB-AlqOLEDs or corresponding OLEECs;

FIG. 2 shows the voltage curve of an NPB-Alq diode in prolongedoperation under constant current;

FIG. 3 shows the decline in luminance of both components with increasedoperating time at constant current; and

FIG. 4 shows the power efficiency of the OLEDs compared over a prolongedperiod.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Reference will now be made in detail to the preferred embodiments of thepresent invention, examples of which are illustrated in the accompanyingdrawings, wherein like reference numerals refer to like elementsthroughout.

FIG. 1 shows the luminance (right-hand axis) and the currentcharacteristic (left-hand axis) of two identically produced NPB-AlqOLEDs or corresponding OLEECs. The difference lies merely in thepretreatment of the TCO, here an ITO layer, with red (round) showing thelayer treated conventionally with oxygen plasma and black (square) thelayer pretreated with perfluorodecyltrichloro-, silane.

The I-V and luminance characteristic of the diodes with substrates fromexamples 1 and 2 are shown in FIG. 1.

The dark currents of the diode with an SAM-coated substrate are somewhathigher compared to the reference diode. In the passage range, the twoorganic light-emitting diodes are virtually identical.

FIG. 2 shows the voltage curve of an NPB-Alq diode in prolongedoperation under constant current. It is evident here in a quite dramaticmanner how the lifetime of the line shown by black squares at the bottomfor the ITO layer treated has increased.

Under the conditions specified in FIG. 2, the diodes were operated atconstant current for 150 hours. The constant current is guided by bothdiodes glowing with equal brightness with luminance in the same order ofmagnitude. The reference diode had an initial luminance of 1000 cd/m2,the SAM diode an initial luminance of 670 cd/m2. While the voltage inthe reference diode rises by more than 60% in order to maintain theconstant current, the voltage remains virtually constant in thecomponent in spite of higher total charge flow.

FIG. 3 shows the decline in luminance of both components with increasedoperating time at constant current.

In the reference OLED (again red and round, the curve falling steeplyeven at the start), a significant collapse in luminance of approx. 10%is observed at the start, which is attributable to the degradation ofthe anode-hole conductor interface. Thereafter, the component stabilizesand the “normal” degradation process of the emitter becomes visible. Inthe case of the OLED (the comparative test could also be conducted witha corresponding OLEEC structure), the initial decline in luminance isnot observed. The somewhat steeper decline after prolonged operatingtime results from the higher current loading overall. As a result of theITO pretreatment with the self-assembly monolayer deposited from the gasphase, the luminous efficiency of the diode is maintained for muchlonger, which significantly prolongs the LT70 lifetime (LT70: decline inthe starting luminance to 70%).

FIG. 4 shows the power efficiency of the OLEDs compared over a prolongedperiod. Here too, the OLED shines again, where a record value comparableto the untreated OLED at the start is maintained virtually over theentire measurement period.

The selection of functioning molecules for the SAM with positive effectson lifetime and efficiency is very limited, as has been demonstratedimpressively in the literature and in in-house tests:

For instance, it has been demonstrated that, instead of trichlorosilane,for example, it also possible to use trimethoxysilane.

The proposals relate to a novel selection for monolayers of organicdielectric compounds on transparent conductive metal oxide surfaces, asused, for example, in the production of organic-based electroniccomponents. The selection achieves completely new orders of magnitude inlifetime of the devices thus produced. Furthermore, it is also possibleto mention many advantageous fields of use of these monolayers, forexample use for corrosion protection, for lithography, etc.

The invention has been described in detail with particular reference topreferred embodiments thereof and examples, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention covered by the claims which may include thephrase “at least one of A, B and C” as an alternative expression thatmeans one or more of A, B and C may be used, contrary to the holding inSuperguide v. DIRECTV, 69 USPQ2d 1865 (Fed. Cir. 2004).

1-13. (canceled)
 14. A method of forming a monolayer on a metal surface,comprising: providing a metal having a conductive metal oxide surface;providing an organic compound having a fluorinated silane group; andbinding the organic compound to the conductive metal oxide surface viathe silane group.
 15. The method as claimed in claim 14, wherein theconductive metal oxide surface is transparent.
 16. The method as claimedin claim 14, wherein the organic compound is represented by thefollowing formula:

where R₁, R₂, R₃ are each independently selected to be Cl, an alkoxy, orOH, X is O, S, NH or absent, n is from 0 to 5, and m is from 0 to 20.17. The method as claimed in claim 14, wherein the organic compound isrepresented by the following formula:

where R₁, R₂, R₃ are each independently selected to be Cl, a methoxy, anethoxy or OH, X is O, S, NH or absent, n is 0, and m is from 5 to 10.18. The method as claimed in claim 14, wherein the organic compound isrepresented by the following formula:

where h and f each independently have a value from 1 to 4, X₁, X₂ and X₃are each independently selected to be 0, S, a halogen, NH or absent, nis from 0 to 2, and m is from 0 to
 15. 19. The method as claimed inclaim 14, wherein the organic compound is a fluorinated straight-chainsilane compound having a silane end, and the organic compound isdeposited in the gas phase to cause the silane end to bond to the metaloxide surface.
 20. The method as claimed in claim 19, wherein gas phasedeposition is performed in a temperature-controllable vacuum chamber.21. The method as claimed in claim 19, wherein the organic compound isdeposited using Chemical Vapor Deposition (CVD) and/or Atomic LayerDeposition (ALD).
 22. A product comprising: a conductive metal oxidelayer; self-assembly monolayer (SAM) formed from a fluorinated silanebonded to the conductive metal oxide layer; and a hole conduction orelectron injection layer conductively connected to the conductive metaloxide layer via the SAM layer without formation of a direct interfacebetween the metal oxide layer and the hole conduction or electroninjection layer.
 23. The product as claimed in claim 22 wherein thesilane is selected from trichlorosilanes, ethoxysilanes andmethoxysilanes.
 24. The product as claimed in claim 22, wherein theorganic compound is represented by the following formula:

where R₁, R₂, R₃ are each independently selected to be Cl, or alkoxy,and OH, X is O, S, NH or absent, n is from 0 to 5, and m is from 0 to20.
 25. The product as claimed in claim 22, wherein the organic compoundis represented by the following formula:

where R₁, R₂, R₃ are each independently selected to be Cl, a methoxy, anethoxy or OH, X is O, S, NH or absent, n is 0, and m is from 5 to 10.26. The product as claimed in claim 22, wherein the organic compound isrepresented by the following formula:

where h and f each independently have a value from 1 to 4, X₁, X₂ and X₃are each independently selected to be O, S, a halogen, NH or absent, nis from 0 to 2, and m is from 0 to
 15. 27. A product comprising: aconductive metal oxide layer; and self-assembly monolayer (SAM) formedfrom a fluorinated silane bonded to the conductive metal oxide layer,wherein the silane is bound on a surface of the metal oxide layer fromthe gas phase.
 28. The product as claimed in claim 27 wherein the silaneis selected from trichlorosilanes, ethoxysilanes and methoxysilanes. 29.The product as claimed in claim 27, wherein the organic compound isrepresented by the following formula:

where R₁, R₂, R₃ are each independently selected to be Cl, or alkoxy,and OH, X is O, S, NH or absent, n is from 0 to 5, and m is from 0 to20.
 30. The product as claimed in claim 27, wherein the organic compoundis represented by the following formula:

where R₁, R₂, R₃ are each independently selected to be Cl, a methoxy, anethoxy or OH, X is O, S, NH or absent, n is 0, and m is from 5 to 10.31. The product as claimed in claim 27, wherein the organic compound isrepresented by the following formula:

where h and f each independently have a value from 1 to 4, X₁, X₂ and X₃are each independently selected to be O, S, a halogen, NH or absent, nis from 0 to 2, and m is from 0 to
 15. 32. A product comprising: atransparent conductive metal oxide surface; self-assembly monolayer(SAM) on the transparent conductive metal oxide surface, theself-assembly monolayer having a head group and an anchor group, theanchor group being attached to the oxide surface; a layer formed from ahole-conducting compound attached to the head group of the self-assemblymonolayer, the hole-conducting compound being selected from the groupconsisting of:N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-dimethylfluorene,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-diphenylfluorene,N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-diphenylfluorene,N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-2,2-dimethylbenzidine,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-spirobifluorene,2,2′,7,7′-tetrakis(N,N-diphenylamino)-9,9′-spirobifluorene,N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine,N,N′-bis(naphthalen-2-yl)-N,N′-bis(phenyl)benzidine,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-9,9-dimethylfluorene,N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-9,9-spirobifluorene,Di-cyclohexane, 2,2′,7,7′-tetra(N,N-ditolyl)aminospirobifluorene,9,9-bis-9H-fluorene, 2,2′,7,7′-tetrakis-9,9-spirobifluorene,2,7-bis-9,9-spirobifluorene, 2,2′-bis-9,9-spirobifluorene,N,N′-bis(phenanthren-9-yl)-N,N′-bis(phenyl)benzidine,N,N,N′,N′-tetranaphthalen-2-ylbenzidine,2,2′-bis(N,N-diphenylamino)-9,9-spirobifluorene, 9,9-bis-9H-fluorene,9,9-bis-9H-fluorene, Titanium oxide phthalocyanine, Copperphthalocyanine, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane,4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine,4,4′,4″-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine,4,4′,4″-tris(N-(1-naphthyl)-N-phenylamino)triphenylamine,4,4′,4″-tris(N,N-diphenylamino)triphenylamine, Pyrazinophenanthroline-2,3-dicarbonitrile,N,N,N′,N′-tetrakis(4-methoxyphenyl)benzidine,2,7-bis-9,9-spirobifluorene, 2,2′-bis-9,9-spirobifluorene,N,N′-di(naphthalen-2-yl)-N,N′-diphenylbenzene-1,4-diamine,N,N′-diphenyl-N,N′-di-benzidine, N,N′-diphenyl-N,N′-di-benzidine, andTri(diphenylbenzimidazoyl)iridium(III) DPBIC.
 33. The product as claimedin claim 32, wherein the self-assembly monolayer functions as an organicelectronic component.
 34. The product as claimed in claim 32, whereinthe self-assembly monolayer functions as an organic light-emitting diodeor an organic light-emitting electrochemical cell (OLEEC).